Diglycidyl ethers

ABSTRACT

Diglycidyl ethers of binuclear, five-membered or six-membered, unsubstituted or substituted, N-hetero-cyclid compounds containing two NH groups in the molecule and containing added-on butene oxide, produced by reaction of binuclear, five-membered or six-membered, unsubstituted or substituted, N-heterocyclic compounds, such as bis-(hydantoin) or bis-(dihydrouracil) compounds, for example 1,1&#39;&#39;-methylene-bis-(5,5-dimethylhydantoin, 1,6-(bis-(5,5-dimethyl-hydantoinyl-3)-hexane or Beta , Beta &#39;&#39;bis-(5,5-dimethylhydantoinyl-3)-diethyl ether, with butene oxide, for example, 1,2-butene oxide, to give monoalcohols or dialcohols, and subsequent glydidylation of the OH groups or of the OH group and the NH group to give the corresponding glycidyl ethers.

United States Patent [191 Habermeier et a1.

[11] 3,821,242 1*June 28, 1974 DIGLYCIDYL ETHERS [75] Inventors: Juergen Habermeier, Allschwil; Hans Batzer, Arlesheim; Daniel Porret, Binningen, all of Switzerland [73] Assignee: Ciba-Geigy AG, Basel, Switzerland Notice: The portion of the term of this patent subsequent to July 25, 1989, has been disclaimed.

[22] Filed: Feb. 24, 1971 21 Appl. No.: 118,499

[30] Foreign Application Priority Data Mar. 5, 1970 Switzerland 3272/70 Oct. 26, 1970 Switzerland 15776/70 [52] US. Cl. 260/309.5, 260/2 EP, 260/2 EA, 260/2 EC, 260/78.4 EP, 260/256.4 C

[51] Int. Cl C07d 49/32 [58] Field of Search 260/309.5

[56] References Cited UNITED STATES PATENTS 3,391,097 7/1968 Williamson 260/309.5 3,449,353 6/1969 Porret et a1 260/309.5 3,542,803 11/1970 Porret 260/309.5

3,592,823 7/1971 Porret 260/309.5 3,629,263 12/1971 Batzer et al 260/309.5 3,631,221 12/1971 Batzer et al 260/309.5 3,679,681 7/1972 Habermeier et a1. 260/3095 FOREIGN PATENTS OR APPLICATIONS 7/1970 Germany 260/309.5

Primary Examiner-Natalie Trousof [5 7 ABSTRACT Diglycidyl ethers of binuclear, five-membered or sixmembered, unsubstituted or substituted, N-heterocyclid compounds containing two NH groups in the molecule and containing added-on butene oxide, produced by reaction of binuclear, five-membered or sixmembered, unsubstituted or substituted, N-

heterocyclic compounds, such as bis-(hydantoin) or 5 Claims, No Drawings DIGLYCIDYL ETHERS The subjectof the US. Pat. No. 3,679,681 are new diglycidyl compounds of the general formula wherein Z and Z independent of one another each denote a nitrogen-free divalent radical which is necessary to complete a five-membered or six-membered, unsubstituted or substituted, heterocyclic ring, A represents a divalent aliphatic, cycloaliphatic or araliphatic radical, and in particular preferably represents an alkylene radical, or an alkylene radical interrupted by oxygen atoms, X X Y and Y each denote a hydrogen atom or a methyl group, and m and n each represent an integer having a value of to 30, preferably of 0 to 4, the sum of m and n having to be at least 1. i

The compounds of the formula (I) are manufactured by reacting compounds of the general formula heterocyclic compounds of the formula (III) with a butene oxide, preferably l,2-butene oxide. 1,2- cyclopentene oxide or l,2-cyclohex ene oxide in the presence of a suitable catalystyields new m'onoalcohols wherein Z Z A, Y Y m and n have the same meaning as in the formula (I), in a single stage or in several stages, with an epihalogenohydrin or thylepihalogenohydrin, such as, for example, epichlorohydrin, a-methylepichlorohydrin or epibromohydrin, in a manner which is in itself known.

The monoalcohols or dialcohols of the general forwherein X X Y and Y each denote a hydrogen atom or a methyl group and Y and Y each denote a B- methyl or ethyl group, with the sum of the carbon atoms in the two radicals Y and Y or Y and Y always having to be 2, or wherein Y and Y or Y -and Y,, to gether denote the trimethylene or tetramethylene radical and wherein Z, and Z independently of one anmula have hitherto not y been described in the other each denote a nitrogen-free, divalent radical literature, and are obtained in a known manner by reacting binuclear N-heterocyclic compounds of the general formula wherein Z,, Z and meaning as in the formula (I), with alkene oxides, preferably ethene oxide (ethylene oxide) or propene oxide (propylene oxide), in the presence of a suitable catalyst. v

rlthe now e ound hatw c n ni sl a N- formula which is necessary to complete a five-membered or sixmembered, unsubstituted or substituted, heterocyclic ring, A represents a divalent aliphatic, cycloaliphatic or araliphatic radical, and in particular preferably represents an alkylene radical or an alkylene radical interf9 m laam.

R: I O 0 R v- The new diglycidyl ethers of the formula (IV) are manufactured by reacting compounds of the general thylepihalogenohydrin, such as, for example, epichlorohydrin, B-methylepichlorohydrin or epibromohydrin, I

in a manner which is in itself known.

- In the single-stage process, the reaction of the epihalogenohydrin with a compound of the formula (V) take place in the presence of alkali, sodium hydroxide or potassium hydroxide being used preferably. In the preferentially used two-stage process, the compound of the formula (V) is condensed, in a first stage, with an epihalogenohydrin, in the presence of acid or basic catalysts, such as preferably tetraethylammonium chloride, to give the halogenohydrin compound, and

thereafter the latter is dehydrohalogenated, in a second stage, by meansof alkalis, such as potassium hydroxide or sodium hydroxide, to give the glycidyl ether.

The addition of the butene oxide, cyclopentene oxide or cyclohexene oxide to one or both NH groups of the N-heterocyclic compounds of the formula (III) can be carried out in the presence of either acid or alkaline catalysts, and per equivalent N group of N-heterocyclic compound of the formula (III) a slight excess over the equivalent epoxide groups of the butene oxide is employed.

Preferably, however, alkaline catalysts such as tetraethylammonium chloride or tertiary amines, are used in the manufacture of monoalcohols and dialcohols of the formula (V) in which the sum of m and n equals 1 or '2. However, alkalihalides, such as lithium chloride or sodium chloride, can also be used successfully for this addition reaction; the reaction also takes place without catalysts.

In the preparation of dialcohols of the formula (V) in which the sum of m and n is greater than 2, it is preferred to start from the simple dialcohols of the formula (V) in which m and n are each I, and to add further butene oxide to the two OH groups of this compound, in

. all bis-(hydantion) compounds or bis-(dihydrouracil) compounds, in which the two N-heterocyclic rings are linked to one another via an alkylene bridge, for example a methylene group, which is bonded to an endocyclic nitrogen atomof each of the heterocyclic rings in question.

A first category of such bis-(hydantoin) compounds 9FPP$l a erelfe m l i.

wherein R R R and R each denote a hydrogen atom or a lower alkyl radical with one to four carbon atoms, or wherein R, and R or R and-R together form a tetramethyleneor pentamethylene radical.

l,1'-methylene-bis-( 5,S-dimethyI-hydantoin), methylene-bis-( S-methyl-S-ethyl-hydantoin l, l methylene-bis( 5-propyl-hydantoin) and l,l methylene-bis-(S-isopropyl-hydantoin) may for example be mentioned.

A further class of such bis-(hydantoin) compounds corresponds t lth 8999 tqrm a (VII) radical, especially an alkyl radical or an alkylene radi-' wherein R R R R R and Rm independently of one another each denote a hydrogen atom or a lower alkyl radical with one to four carbon atoms.

1,1'-Methylene-bis (5,o-dihydrouracil), l,l methylene-bis-( 6-methyl-5,o-dihydrouracil) and 1,1 methylene-bis-(S,5 dimethyl-S,6-dihydrouracil) may be mentioned.

The diglycidyl compounds according to the invention,of the formula (IV), react with the usual curing agents for polyepoxide compounds and can therefore be crosslinked, or cured, by addition of such curing agents, analogously to other polyfunctional epoxide compounds or epoxide resins. Possible curing agents of this nature are especially polycarboxylic acid anhydrides, such as, for example, hexahydrophthalic anhydride or phthalic anhydride, and also polyamines, such as for example triethylenetetramine or 3,5,5-trimethyl- 3(amin0methyl)-cyclohexylamine.

The sszp in m.. s r e ab vealcmployed in the 5,5-dimethyl-of surface protection, the electrical industry, laminating processes and the build-- ing industry.

In the examples which follow, unless otherwise stated, parts denote parts by weightand percentages denote percentages by weight. The relationship of parts dissolved'in 300 ml of dimethylformamide and the solution is stirred at 65 C. 144.2 g of 1,2butene oxide (2.0 mol) are added over the course of one hour. Thereafter, the reaction mixture is stirred for a further 20 hours at 75 C and cooled to room temperature, andthe slight cloudiness originating from the hydantoin raw material is removed by filtration. the clear solution is completely by volume to parts by weight is as of the millilitre to the gram.

To determine the mechanical and electrical properties of the curable mixtures described in the examples which follow, sheets of size 92X 41 X 12 mm were manufactured for determining the flexural strength, de-

flection, impact strength and water absorption. The test specimens (60 X 10 X 4 mm) for determining the water absorption, and for the flexural test and impact test (VSM 77,103 and VSM 77,105 respectively were machined from the sheets.

Test specimens of sixes 120 X 15 X 10 mm were in each case cast for determining the heat distortion point according to Martens (DIN 53,458).

Sheets of sizes 120 X 120 X 4 mm were cast for determining-the arcing resistance.

MANUFACTURE or THE STARTING SUBSTANCES Example A: 1,1 -Methylene-bis-[ 3-(2-hydroxy-nbutyl )-5 ,S-dimethylhydantoin] A suspension of 134.1 g of l,l'-methylene-bis-(5,5- dimethylhydantoin) (0.5 mol) and 2.68 g of lithium chloride in 350 ml of dimethylformamide is stirred at 60 C. 83.0 g of 1,2-butene oxide (1.15 mols) are added dropwise over the course of 30 minutes; the mixture is then stirred for a further 4 /2 hours at 75 C,

' whereupon a clear solution is produced. When the latter has been cooled to room temperature, it is filtered, and the clear, colourless solution is concentrated at 70 concentrated on a rotary evaporator at 75 C, under a waterpump vacuum; thereafter, the residue is dried to constant weight at 0.2 mm Hg and 90 C. 206.5 g of a pale yellow, clear, transparent, highly viscous substance'(85.8 percent of theory) are obtained. consisting mainly of the compound of the following structure:

CH: 0 CH3 Example C: B, B-Bis-[1-(2 -hydroxy-n'-butyl)-5,5-

dimethyl-hydantoinyl-3 ]-diethyl ether.

A solution of 375 ,g of B,B-bis-(5,5 dimethylhydantoinyl-3 )-diethyl ether (1.15 mols) and 1.95 g of lithium chloride in 500 ml of dimethylfonnamide is prepared at 60 C. 332.0 g of'1,2-butene oxide C on a rotary evaporator, under 15 mm Hg. Thereafter,

the residue is dried to constant weight at 90 C/ 10.1 mm Hg. 206.1 g (100 percent of theory) of a colourless, clear, highly viscous resin are obtained; its IR spectrum no longer shows any N-H absorptions, but

displays the OH frequencies. Elementary analysis shows the following:

found 7 calculated 13.6%N .l3.S8%N 7.9 71 H 7.82 7: H

Accordingly, the new diol has the following structure:

Example B 1,6-Bis-[1-(2-hydroxy -n-butyl)-5 ,5 dimethyl-hydantoinyl-3]-hexane.

169.2 g of 1.6-bis-(5 ,5 -dimethylhydantoinyl-3')- hexane (0.5 mol) and 0.848 g of lithium chloride are (4.60 mols) are added dropwise to this solution over the course of 45 minutes, whilst stirring. The reaction mixture is stirred for a further 15 hours at C and filtered, and the clear, colourless solution is concentrated at 70 C on a rotary evaporator, under a waterpump vacuum. The residue is then dried to constant weight under 0.1 mm Hg at C bath temperature. A

-highly viscous, clear, transparent, pale yellowishcoloured substance is obtained in percent yield (541.2 g). The infrared spectrum shows,'through the absence of the amide N-H absorption and through the presence of a strong OH absorption, that the new substance has the following structure:

The proton-magnetic resonance spectrum (60 Mc H-NMR, recorded in CDCl;, against tetramethylsilane the internal standard) shows, through the presence of the following signals, that the formula given below is to be ascribed to the product obtained: =5.15 Singlet N-CE -N 2 protons =3.54'.6 Multiplet N-CE-Cg-OH 6 protons =1.32.5 Multiplet of remaining CH3- and CH:-- protons (28) E HQIC on; 1 N

H; 0 CH 0 Example E: 1,1-Methylenebis-(3-(2-hydroxy-nrfisopm yl d l- A suspension of a 74.1 g of 1,1" -methylenebis-(-isoprgpylhydantoin) (0.25 mol), 200 ml of dimethylformamide and 0.53 g of lithium chloride is stirred at 65 C. 49.6 g of 1,2-butene oxide (0.688 mol) are added dropwise thereto,

over the course of 120 minutes. The temperature is then raised to 100 C over the course of 60 rr in;

l CH:

' utes and the mixture is allowed to react for a further 9 hours whilst stirring, a clear solution being produced thereby.

This is cooled to room temperature and filtered, and the filtrate is concentrated to dryness at 80 C/15 mm Hg. Thereafter, the residue is treated at 90C/0.2 mm Hg until constant weight is reached. 110.5 g (corresponding to 100 percent of theory) of a colourless, clear, viscous substance are obtained, consisting mainly of 1,1 -methylenebis-(3-[ 2"-hydroxy-n-butyl]-5- isopropylhydantoin). Example F: butyl]-5,55,6-dihydrouracil) A suspension of 148.2 g of l,l'-methylenebis-(5,5- dimethyl-5,6-dihydrouiaciITT075 iiiBlTir'iZFU'nilFt'HT methylformamide is stirred with 1.06 g of lithium chloride at 65 C. 99.2 g of 1,2-butene oxide (1.376 mols) are added dropwise over the course of 2 hours, whilst stirring. The temperature is then raised to 103105 C over the course of 150 minutes, a clear, colourless solu- 5 1,l-Methylenebis-(3-[Z-hydroxy-ntion is thereby produced. This is stirred for a further 10 less, viscous liquid.

1. Manufacturing Examples Examples 1: 1,1 -Methylene-bis-[ 3-(2-glycidyloxy-nbutyl)-5,5-dimethylhydantoin] I 205.9 g of the 1.1'-methylene-bis-[3-(2-hydroxy-nbutyl)-5,5-dimethylhydantoinl manufactured according to Example A (0.499 mol) together with 925 g of epichlorohydrin 10 mols) and 2.5 g of tetracthyleneammonium chloride are stirred for 1 hour at C. A circulatory distillation is then started at 60 C/60-90 mm Hg, with vigorous stirring, and 103.0 g of 50 percent strength aqueous sodium hydroxide solution are slowly added dropwise over the course of 2 hours. At the same time, the water present in the reaction mixture is continuously azeotropically removed from the circuit and separated off. After the addition of the sodium hydroxide solution, the mixture is distilled for a further 15 minutes to remove the last remnants of water. The sodium chloride formed is filtered off and rinsed with ml of epichlorohydrin, and the combined epichlorohydrin solutions are extracted by shaking with 200 ml of water, so as to remove traces of sodium hydroxide and sodium chloride. The organic phase is separated off and completely concentrated at 60 C on a rotary evaporator under a slight vacuum; the residue is then dried to constant weight at 80 C under 0.1 mm Hg. I

220.4 g (81.2percent of theory) ofa light brown, viscous, liquid epoxide resin containing 3.2 epoxide equivalents per kg (84.3% of theory) are obtained, corresponding substantially to the following formula:

0 Hz 11 u I O O CH:

Example 2. 1 ,613154 1- Z-glycidyloxy-n-butyl -5,5-

5 azeotropically removed from the circuit and separated off. Thereafter, the sodium chloride formed is filtered off and rinsed with 60 ml of epichlorohydrin, and the combined epichlorohydrin solutions are extracted by shaking with ml of water, to remove traces of sodium hydroxide and sodium chloride. The organic phase is separated off and completely concentrated on a rotary evaporator at 60 C, under a slight vacuum. Thereafter, the residue is dried to constant weight at 80 C under 0.1 mm Hg.

210.5 g of a pale yellow, viscous resin (85 percent of theory) are obtained. The epoxide content is 2.68 equivalents/ kg (corresponding to 79.6 percent of theory). The total chlorine content is 0.7 percent.

517.0 g of the B-bis-[1-(2-hydroxy-n-butyl)-5,5-

dimethylhydantoinyl-3]-diethyl ether manufactured according to Example C (1.1 mols) are mixed with 2,035 g of epichlorohydrin (22 mols) and 5.45 g of tetraethylammonium chloride. This 7 mixture is stirred for 1 hour at 90 C. It is then dehydrohalogenated as described in Example 2, using 228.7 g of 50 percent strength aqueous sodium hydroxide solution and azeotropically removing water at 60 C. Working up is also effected in ac-. cordance with Example 2. 543.0 g (85 percent of theory) of a clear, viscous resin are obtained. The epoxide content is 2.65 equivalents/kg (77 percent of theory). The total chlorine content is 1.lpercent. Example 4: 1,1 -methylene-bis-[ 3-( 2- glycidyloxycyclohexyl)-5,5-dimethylhydantoin] A mixture of 232 g of the 1,1-methylene-bis-[3-(2- hydroxycyclohexyl)-5,5-dimethylhydantoin] manufac tured according to Example D (0.5 mol), 2.48 g of tetramethyl-ammonium chloride and 1,388 g of epichlorohydrin mols) is heated to the boil at 1 16 1 17 C for 60 minutes, with good stirring.

The' mixture is then dehydrohalogenated over the course of 2 hours with 100g of 50 percent strength aqueous sodium hydroxide solution, in accordance with Example 1. The working up and the isolation of the reaction product are also effected exactly as in Example 1.

' 193 g ofa crystallising, yellowish melt (66.5 percent of theory) are obtained. The epoxide content is 2.75 epoxide equivalents per kg (corresponding to 80 percent of theory). The proton-magnetic resonance spectrum shows the epoxide signals at 8 2.55 3.00 and ,8 3.10 3.20, and is in other respects, apart from the signals of 01-1 groups, identical with the spectrum of the starting product. Example 5 v 88.1 g of the 1,1 -methylene-bis(3-[2-hydroxy-nbutyl 1-5-iso awn;yazihtammaraetiriaiaeoiaifig to Example E (0.2 mol), 925 g of epichlorohydrin and 1.5 g of 50 percent strength aqueous tetraethylammonium chloride solution are subjected to an azeotropic circulatory distillation at 60 C. reaction temperature and 60-85 mm Hg vacuum, whilst stirring; at the same time, the bath temperature is 142145 C. When the distillation is well under way, 40 g of 50 percent strength aqueous sodium hydroxide solution are added dropwise over the course of 120 minutes, and at the same time the water present in the reaction mixture is continuously separated off. After completion of the addition of sodium hydroxide solution, distillation is continued until the last traces of water have been separated off; 24 ml (85.5 percent of theory) are found. Working up is carried out analogously to Example 2, and a clear, liquid, practically colourless resin of 2.96 epoxide equivalents/kg is obtained.

Example 6 88.1 g of 1,l-methylenebis-(3-[2 -hydroxy-n-butyl]- 5,5-dimethyl-5,6-dihydrouracil) (0.2 mol) are reacted with 925 g of epichlorohydrin, using 1.5 g of 50 percent strength aqueous tetraethylammonium chloride solution as an auxiliary. in accordance with Example 5, the

dehydrohalogenation being carried out with 40 g of 50 percent strength aqueous sodium hydroxide solution, precisely in accordance with Example '5. Working up takes place as has been described in Example 2. 88 g (80 percent of theory) of a colourless, liquid, clear epoxide resin having 3.02 epoxide equivalents per kg are obtained.

11. EXAMPLES OF USES Example I 1 12.5 gof the 1,l'-methylene-bis-[3-(2 -glycidyloxyn-butyl)-5,5-dimethylhydantoin] manufactured according to Example 1 having 3.2 epoxide equivalents/kg, are mixed with 47.3 g of hexahydrophthalic anhydride at C. The homogeneous, clear melt is cured in aluminium moulds over the course of 3 hours at C and 12 hours at C.

Mouldings having the following mechanical properties are obtained:

Flexural strength (VSM 77,103) 9.61 kp/mm" Deflection (VSM 77.103) 3.7 mm lmpact strength (VSM 77.105) 12.25 cntkp/cm Water absorption (4 days/20C) 0.58 7r 10.04 lap/mm Flexural strength (VSM 77.103) Impact strength (VSM 77.105) 13.5 cmkp/cm" Water absorption (4 days/20C) Example 111 302 g of the ,8, B'-bis-[1-(2'-glycidyloxy-n-butyl)- 5,5-dimethylhydantoinyl-3]-diethyl ether manufactured according to Example 3, having 2.65 epoxide equivalents/kg, are worked into a homogeneous melt with 106 g of hexahydrophthalic anhydride at 70 C. Curing is carried out in aluminium moulds of 4 mm wall thickness, over the course of 3 hours at 80 C and 12 hours at 150 C.

Moulding having the following properties are obtained:

Tracking resistance (VDE 0303) KA3b Arcing resistance (DIN 53.484) L4 Breakdown voltage, 23C (instantaneous value) 221 kV/cm Dielectric loss factor (50 c/s) tg 8 at 24C 0.008

at 40C 0.037

Volume resistance D' 24C 2.4 X 10' 11. cm

We claim: 1. A diglycidyl ether of the formula:

3 ,821 ,242 l1 12 R, o i R1 0 ma ls-ii l i e m 0 O -CCHr-0t 1H-oH-N AN\ N-cH 3HC0H:( I

1 Y1 Y1 \C/ C/ Y 'f Y1 X1 0 R1 I'M 0 /O i I---R1 R1C* g /O\ OHzCOH O-CH-CHI 'I I I-CHz-N I ICH?HOGHz? ii Y2 Y1 fit f! Y: X1 N. m mlmmeuw 7 e.

wherein i 2. l,l-Methylene-bis-[3-(2 -glycidyloxy-n-butyl)- X is hydrogen or methyl; Y is hydrogen, Y is ethyl, 5,5-dim thylh dam0in] or wherein Y and Y together are trimethylene or 3 1 i 1 2 5' 5' tetramethylene; R and R is hydrogen or lower dimethyhydantoinyl-3']-hexane. alkyl of one to four carbon atoms or R and R 4. 3, B-Bis-[l-(2 -glycidyloxy-n-b1ityl)-5,5- together are tetramethylene or' penetamethylene; di th h d t i l-j,]-di th l ether and A is alkylene of one to 12 carbon atoms or 5. l,1-Methylene-bis-[3-(2 -glycidyloxycyclohexyl)' lower alkylene interrupted by one oxygen atom '5,5 di th lh d m in] 

2. 1,1''-Methylene-bis-(3-(2 -glycidyloxy-n-butyl)-5,5-dimethylhydantoin).
 3. 1,6-Bis-(1''-(2 -glycidyloxy-n-butyl)-5'',5''-dimethyhydantoinyl-3'')-hexane.
 4. Beta , Beta ''-Bis-(1-(2 -glycidyloxy-n-butyl)-5,5-dimethyhydantoinyl-3)-diethyl ether.
 5. 1,1''-Methylene-bis-(3-(2 -glycidyloxycyclohexyl)-5,5-dimethylhydantoin). 